Nitrogen containing indan derivatives



Unite dtates 3,283,016 NITROGEN C(DNTAENING MAN DERIVATIVES Thomas F. Wood, Wayne, and John T. Angiolini, Uifton, N..l., assignors to The Givaudan Corporation, New York, N.Y., a corporation of New Jersey No Drawing. Filed Sept. 28, 1964, Ser. No. 399,901 6 Claims. (Cl. 260-4545) This invention relates to novel and useful nitrogen-containing indan compounds and methods for their preparation.

An object of this invention is the provision of a novel class of compounds having various uses in the arts.

A specific object of this invention is the provision of compounds having effective and superior properties as herbicides.

A further object of the present invention is to provide a process for easily making the novel compounds of this invention in an inexpensive manner from low-cost and readily-available materials.

The foregoing and other objects of this invention have been attained by providing compounds which are members of the group encompassed by the following general formula:

E Rm lNA ln wherein R is a member selected from the group consisting of H and alkyl radicals having from 1 to 3 carbon atoms; R is a member selected from the group consisting of alkyl radicals having from 1 to carbon atoms and cycloalkyl radicals; A is a member selected from the group consisting of O and H; m is an integer from 2 to 3; n is an integer from 1 to 2, with the proviso that at least one R must be H and the further proviso that where more than two of the R s are H, then m can be an integer from 1 to 3; 4,6 dinitro 2 ethyl 1,1,3,3,5 pentamethylindan and 4,6 dinitro 5 ethyl 1,1,3,3 tetramethylindan.

Examples of compounds coming within the scope of this invention are the following:

5 ,7 -dinitro-1,1-dimethyl-6-isopropylindan 5,7-diamino-1,1-dimethyl-6-isopropylindan S-amino-1,1-dimethyl-6-isopropyl-7-nitroindan or 7-amino- 1, 1-dirnethyl-6-isopropyl-5-nitroindan 5,6-dinitro-7-isopropyl-1,1,4-trimethylindan 5 ,6-dinitro-7-isopropyl-1,1,2,4-tetramethylindan 5,6-diamino-7-isopropyl-l,1,4-trimethylindan 5,7-dinitro-1,1,4,6-tetramethylindan 5,6-dinitro-1,1,4,7-tetramethylindan 1,1-dimethyl-5,7-dinitro-6-ethylindan 5 ,7-dinitro-1,1,2,4,6-pentamethylindan 6-t-butyl- 1 l -dimethyl-5 ,7 -dinitroindan 6-sec. butyl-1,1-dimethyl-5 ,7-dinitroindan 1,1 -dimethyl-5 ,6-dinitro-4-ethyl-7-isopropylindan 4,6-diisopropyl-l l-dimethyl-S ,7 -dinitroindan 5-t-butyl-4,6-dinitro-1,1-dimethyl-7-isopropylindan 5 (and 7 -nitro-1, 1,4,6-tetramethylindan 1,1-dimethyl-6-isopropyl-5-(and 7) nitroindan S-nitro-l,1,4,6,7-pentamethylindan 7-isopropyl-5-nitro-l,1,4-trirnethylindan 5 -ethyl-6-nitrol l ,3 ,3-tetramethylindan 4,6-diisopropyl-l,l-dimethyl-S-nitroindan 4,6-dinitro-5-ethyl-1,l,3,3-tetramethylindan 4,6-dinitro-2-ethyl-l l ,3 ,3 ,5 -pentamethylindan 3,283fil5 Patented Nov. 1, 1966 The nitrogen-containing indan derivatives disclosed herein are pale yellow to orange colored solids and in some cases pale yellow viscous liquids which have low vapor pressure, are free of objectionable odor, and are readily soluble in the organic solvents commonly used for dissolving herbicidal materials. They are readily purified by crystallizing from alcoholic solutions or from aqueous alcoholic solutions and in some cases by vacuumdistillation.

It has been found that the compounds of this invention are useful for various purposes. Some of the compounds have properties making them suitable for use in perfumery, e.g., as musk odorants. Surprisingly, our compounds have been found to possess properties making them suitable as superior, selective, herbicides, particularly on a pre-emergence basis, and as plant growth regulants. The utility of our compounds is enhanced by the fact that, as contrasted to known commercially available herbicides, they do not have objectionable odors, are nonirritating to the skin and have very low toxicity.

The term pre-emergence means that the compounds are applied, in known manner, to the soil prior to emergence of the weed species sought to be controlled. As used herein, the term includes the application of a herbicidal compound falling within the scope of this disclosure to areas wherein useful or desirable plants are either growing or have been sown, but where the undesirable plants sought to be controlled have not as yet emerged.

The herbicidal activity of the compounds of the present invention is demonstrated by the following tests. Seeds selected from at least two types of common weed varieties such as wild oats, cheatgrass, foxtail, barnyard grass, crabgrass, nut grass, Johnson grass, curled dock, yellow rocket, chickweed, pigweed, velvet leaf and lambsquarter were planted in soil under greenhouse conditions. Immediately after planting, the soil surface was sprayed with aqueous suspensions of these compounds so as to supply the equivalent of 16 lbs. of the compound under test per acre of soil surface. The aqueous suspensions were produced by stirring acetone and/or alcohol solutions of these compounds into water. Three weeks after spray application the herbicidal activity of these compounds was determined in comparison with untreated control areas.

All of the compounds exhibit beneficial pre-emergence herbicidal activity against noxious weeds and grasses; some inhibit germination of only certain weed and grass species; others exhibit a broader spectrum of inhibition. In other words, a high degree of selectivity is shown by this family. For this reason these compounds are of great value in the elimination of weeds and grasses from economic crops such as corn, beans, soybeans, rice and others; some individual members being especially effective in certain specific crops.

The nitro and amino derivatives of this invention are conveniently and economically prepared from the parent alkylindan hydrocarbons. Nitration using more or less standard techniques will produce the monoor dinitroderivatives as desired.

Complete or partial reduction of the nitro derivatives will produce the corresponding monoamino, diamino or nitroamino derivatives as the case may be. In many cases, the parent hydrocarbon may be mainly converted to the dinitroderivative by treatment with a great molar excess of fuming (98%) nitric acid alone. However, by this method considerable oxidation often occurs as a side reaction resulting in lowered yields and may lead to excessive coloration in the product. We prefer to prepare dinitroderivatives by adding one mole of the hydrocarbon slowly with good agitation to a mixed acid composed of 5.5 to 6 moles of 98% nitric acid and 9.5 to 11.0 moles of 93% sulfuric acid while cooling to maintain a reaction 3,283,016 a At di-sec. butylindan and di-cyclohexylindan are prepared by temperature of 20 to 25, preferably to 18. The molar ratios of the mixed acids may be varied considerthe procedure of Pokrovskaya and coworkers. E. S. Pokrovskaya and T. G. Stepantseva, J. Gen. Chem..

ably in the process but appreciable reduction of the nitric acid will lead to substantial amounts of mononitroderiva- U.S.S.R., 9, 1953 (1939); i-bid., Tr. Inst. Netti, Akad.

tive which naturally gives a reduced yield of dinitrode- Nauk S.S.S.R., 1, No. 2,300 (1950). E. S. Pokrovskaya and R. Y. Sushchik, J. Gen. Chem. U.S.S.R., 9, 2291 (1939); Patinkin, S. H. and B. S. Friedman, Friedel- Crafts and Related Reactions, vol. II, Part I, Interscience Publishers, New York, pages 72-3 (1964).

2. Reduction of 1-indan0nes.-This general reaction for the preparation of indans is carried out as follows:

rivative. Increasing the nitric acid above the recommended 6 moles offers no advantage and results in unnecessary waste of the acid. The sulfuric acid concentration may be varied but decreased amounts will result in lower yields and greater amounts offer no appreciable advantages and Waste the excess acid.

For preparation of mononitroderivatives it is possible The reduction may be carried out by the following to modify the nitration process by reducing the nitric methods: acid at least one-half and using sulfuric acid of lesser (a) Reduction 'by zinc and hydrochloric acid (Clemstrength than 93%, such as 75 to 85% and get fair yield mensen).

(b) Reduction by hydrazine in the presence of a base (WolflF-Kishner), For example see Ferrero and Helg., Chim. Acta, 42, 2111 (1959).

(c) Catalytic hydrogenation.

The methods of reducing carbonyl are well-known procedures familiar to chemists skilled in the art and of the mononitroderivatives. However, in order to get substantially quantitative yields of the mononitroderivaatives we prefer to use the procedure developed several years ago by Carpenter et al. (J. Org. Chem., 16, 603 (1951)). Here nitric acid (2.5 moles, 98%) is added to a solution of 8 moles of acetic acid and 4 moles of acetic anhydride, keeping the temperature below need not be discussed further. The hydrocarbon, either alone or dissolved in part of The l-indanones required are readily obtained by the the acetic acid, is added at temperatures varying from procedures previously reported in the literature. -30 to +30-, preferably from 10 to +20". The combination acy'lation-alkylation procedure of In all cases upon completion of the nitration the re- Hart and T bbe, J. Am. Chem. Soc., 72, 3286 (1950) reaction mixture is quenched in ice, and the product taken sults in l-indanone derivatives of the yp needed- For up in benzene, washed with Water, then with 5% sodium example from P' there is Obtained: hydroxide until the washes are free of color, then wi 40 4,7-dimethyl-1-indanone, 2,4,7-trimethyl-l-indanone, water to neutrality and the solvent removed. The remain- 3,4,7-t i th 1-l-i d t ing crude product is then crystallized from an appropriate Similarly many other homologs may be prepared 5mm solvent f ing With other dior tri-substituted benzenes using many In cases Where the correspond ng amin Of dlallnno different cyclialkylati on agents. I. C olonge and L. Pichat, derrvauves are desired the reductions can be effected by 40 B 11 s Chi 1949, 423, describe the preparation of the wellknown procedures of reduction with iron filings 3,3,iltetramethfl-Lindanone fro metaxylene and iand dilute acid, hydrogenation catalyzed by Raney nickel, met'hylacrylic acid. or hydrogenation catalyzed by palladium on carbon. We 3. Cyclodehydration method:

R R 1 1 z i /R2 R4 /R1 ?H R\ R 1 R C C c R2 R 2. O 1-: so 2 1 R R R prefer the latter reduction method since this results in This method is the most versatile of all for the prepaexcellent yields with a minimum of by-products. ration of substituted indans. It was first extensively in- For conversion of dinitroderivatives to aminonitro 9 vestigated by R. O. Roblin, Jr., D. Davidson and M. T. compounds we use the well-known reaction which em- Bogert, J. Am. Chem. Soc., 57, 152 (1935), who preploys sodium sulfide or sulfhydra-te in aqueous or aquepared l-rnethyl-l-ethylindan, 1,1,2-trimethylindan, 1,1-dious alcoholic solutions at reflux temperature to selecmethylindan, 1,1,3-trimethylindan and 1,1,3,3-tetra-methtively reduce one of the nitro groups to amino group. y-lindan. Since this early work the method ha been ex- The parent indan hydrocarbons required for the prepa- 5 tensive'ly used by others. For example, L. I. Smith and ration of the compounds of this invention are readily pre- L. J. Spillane (J. Am. Chem. Soc., 65,207 (1043), prepared by the many procedures recorded in the chemical pared l,1,3,3,4,6-hexamethylindan by the cyclo-dehydraliterature. tion technique. Weber and co-workers have synthesized The procedures most commonly employed are the fol- 1,1,3,5-tetramethyl 3 n-propylindan and 1,1,3,5-tetr-alowing: methyl-3-isobutylindan.

1. Diand tit-alkylation 0f indans.Direct polyalkylation of indan can be carried out in the conventional manner using regular Friedel-Crafts catalysts or pr-otonic acid alkylation catalysts (e.g. H F H PO H 50 For example 4.5,6-tri-isopropyl indan 4,5,6-tri-cyclohexylindan,

4. Cycle-addition of olefins to styrenes.-This general method for the preparation of poly-alkylated indans by reaction of styrenes and olefins in the presence of sulfuric acid was disclosed in US. Patent 2,851,501.

Polyalkylindans useful for preparing acyl derivatives.

of herbicidal value may be similarly obtained by employ- 7. Indans by cycle-addition of 1, 3-butadienes to aroing suitable substituted styrenes and olefins: For example: matic hydr0carb0ns.A one-step method for the prepa- 0., 2, 4-tr imethyl- Z-methyl-Z- styrene butene CH COOH a-methyl-Z, 4-diisobutylene isopropylstyrene (Z-methyl-l -propene) 5. Cyclo-addition of olefins to suitably substituted pration of polyalkylated indans was developed by the prescymylcarbonium i0ns.-Polyalky1 indans useful for the em inventors and is disclosed and claimed in our copreparation of the herbicidally active acyl derivatives may pending US. patent applications, Serial No. 107,023, be prepared as follows:

2, 4-diethylcumy1- isobutylene c arbonium ion 2, 4-dimethylcumylz-methyl-vl -penten'e carbonium ion 2, 4-dimethylcumy1- Z-methyl-Z-pentene carbonium ion 6. Hydrogenation of substituted indenes. filed May 2, 1961 and Serial No. 229,867, filed October 7 11, 1962. The latter application is a continuation application of Serial No. 65,261 and of Serial No. 65,290, both filed on October 27, 1960.

This novel reaction may be outlined as follows:

1 R R +CH c cH H2504 1 R CH3 5 where R=H or CH and R =H, alkyl radicals of 1 to 6 atoms, or cycloalkyl radicals.

The invention is further illustrated by the following examples, without, however, limiting it to them. All temperatures are in degrees centigrade. All melting points and boiling points are uncorrected.

Example 1 .-5 ,7-dinitr-1 1-dimethyl-o-isopropylindan Into a rapidly stirred mixture of 308 g. of 93% sulfuric acid and 684 g. cumene at S there was slowly added dropwise a solution of 115 g. of isoprene in 200 g. cumene at such a rate that the reaction temperature could be maintained at to 0 throughout the feed. Stirring was continued at 0 for 40 minutes after the feed was complete. After allowing to settle, the lower sulfuric acid layer was discarded and the remaining oil layer was washed successively with water, 5% caustic soda solution and 5% bicarbonate of soda solution. The washed solution was then subjected to vacuum-distillation, yielding, besides recovered cumene, 1, 1-din1ethyl-6-isopropylindan as a colorless liquid, B.P. 7577 (3 mm.), 12 1.5084, sp. gr. /25=0.8986, amounting to 168 g. The vapor-phase chromatogram indicated a purity of greater than 95%.

This hydrocarbon (168 g.) was slowly added dropwise to mixed acid, prepared from 1000 g. of 93% sulfuric acid and 336 g. of 98% nitric acid with agitation and cooling to keep the temperature at 17 to 19 during the nitration. Crystals of the product separated during the nitration. The batch was then quenched on 1000 g. of ice-water. The crystalline product was filtered off and washed thoroughly with water. It was then dissolved in 600 ml. of benzol and the resulting solution washed successively with Water, dilute caustic soda solution and again with water to neutrality. There remained 236 g. crude crystalline product after evaporation of the benzene. This was recrystallized from 2000 ml. of methyl alcohol at 5 to give 184 g. of pale yellow crystals, M.P. 124- 125.2.

Analysis. Calcd. for C I-1 N 0 C, 60.42; H, 6.52; N, 10.07. Found: C, 60.04;-H, 6.41; N, 10.03.

Example 2.5,7-diamin0-1, 1-dimethyl-6-is0- propylindan 1,1-dimethyl-6-isopropyl-5, 7-dinitroindan (50 g.), suspended in 300 ml. of methanol, was hydrogenated in the presence of 1 g. of palladium on charcoal (5% moist) in a rocking autoclave at a temperature of 50 C. and a pressure of 50 lbs. of hydrogen. After 24 hours, the absorption of hydrogen (271 lbs.) stopped. Since raising the temperature to 80, increasing the pressure to 60 lbs. and addition of 2 g. of new catalyst did not induce further absorption, the solution was filtered from the catalyst.

The filtrate was concentrated to a volume of ml. by distillation in coarse vacuum. The concentrate was poured into 800 ml. of agitated water. A solid formed which was filtered, washed with water and dried at at- 77.23; percent H, 10.44; percent N, 12.97. M.W. 218.33.

Example 3.-5-amin0 1,1 dimethyl 6 isopropyl 7- nitrozndan or 7 amino 1,1 dimethyl 6 isopropyl- 5-nz'lr0indan 1,1-dimethyl-6-isopropyl-5,7dinitroindan (50 g.) was suspended in 400 ml. of agitated methanol. Sodium sulfhydrate (NaI-IS-2H O, 27 g.) dissolved in 400 ml. of methanol was added over a period of 45 minutes. The temperature rose from-28 to 32 C.

The whole was agitated and refluxed for one hour. A brown solution, containing a fine solid, formed. About 300 ml. of methanol were removed by distillation in coarse vacuum.

The concentrate was poured into 3.5 11. of water. A turbid yellow solution formed which, on standing, separated a yellow solid. The solid was filtered, washed with Water and dried at atmospheric pressure. Yield: 26.4 g.; color: orange. It was recrystallized from a mixture of 250 m1. of SD. alcohol No. 30 and 50 m1. of water in the presence of 14 g. of Darco, Yield: 17.2 g.; M.P.: 106110; color: orange.

Analysis for C I-1 N 0 Calcd: percent C, 67.71(; percent H, 8.12; percent N, ll.28 Found: percent C, 67.50; percent H, 8.57; percent N, 11.17. M.W. 248.32.

Example 4.5,6-dinitr0-7-is0propyl-1,1,4-trimethylindan Into a vigorously-agitated suspension of 400 g. of 93% sulfuric acid and 1,000 g. p-cymene cooled to 2, there was slowly added, dropwise, a solution of g. isoprene in 200 g. p-cymene over a 4 /2 hr. period while the temperature was kept at 2 to 1 Stirring was continued for 40 minutes after the feed. The mixture was allowed to settle and the lower sulfuric acid layer was separated and discarded. The remaining oil layer was washed successively with 200 ml. of water, 100 ml. of aqueous 5% caustic soda solution and 1.00 ml. of 5% aqueous sodium bicarbonate solution. The excess pcymene was distilled oil: (20 mm.) and the residual liquid distilled under high vacuum to yield as the main product a colorless liquid, B.P. 97-104" (2.2 mm.), n 1.5161 to 1.5175, sp. gr. 25/25=0.9188, amounting to 248 g. Upon careful refractionation the product boiled mainly at 99-100 (2.1 mm.). This hydrocarbon was shown to have the structure, 7-isopropyl-1,1,4-trimethylindan by study of the infrared and nuclear magnetic resonance spectra, its vapor-phase chromatogram. Final proof was its completion of the hydrogenation the catalyst was resynthesis by analternate method as follows: moved by filtration. The alcohol was evaporated off CH3 HCHO 0 "hexamine" 3 C\=O HCl 7 CH CH0 CH CI CH P- y n /CH 11 H MgI 04R --H O CH 7-isopropy1-l, 1, 4- trimethylindan Nitration of the hydrocarbon with mixed acid by the 30 leaving a dark colored crystalline residue melting at 146 technique described above in Example 1, produced in good to 160. The crude product exhibited herbicidal activity yield an odorless dinitro derivative, M.P. l51152. and was suitable for this use without further purification.

Analysis.-Calcd. for C H N O C, 61.70; H, 6.85; N, 9.58. Found: C, 62.00; H, 6.80; N, 9.52.

The acetyl derivative was prepared by acetylation in 1,1,4,6-tetramethylindan, produced by the cyclo-addition Example 7.5,7-dinitr0-l,1,4,6-tetramethylindan the presence of aluminum chloride using acetyl chloride! of isoprene to meta Xylene in the presence of sulfuric acid It was obtained as a colorless, odorless solid, M.P. 71- using the molar ratios and operating conditions disclosed 72.5. in Examples 1 and 4 above, was nitrated with mixed acid Analysis.-Calcd. for C H O: C, 83.60; H, 9.87. by the technique disclosed in Examples 1 and 4. A pale Found: C, 83.58; H, 9.69. yellow, odorless, dinitroderivative, 5,7-dinitro 1,1,4,6-

tetramethylindan, was obtained, M.P. 9293.5 (from Example 5 Py methanol). This compound was active as a pre-emergence 1,1,2,4-letramethylindan herbicide Cyclo-addition Of 2,341imethyl-1,3-butadiene t0 p-cyfor 0131116912041 (3, 5997; 699; memo was effected by the general method disclosed above Found: 59-49; H, 5-99; N, m Examples 1 and h resuhmg hydwcarbon 7480' Example 8.5,6-dinitr0-1,1,4,7-tetramethylindan propyl-l,l,2,4-tetramethyl1ndan, was obtained as a colorless liquid, 13.1. 98-100 (2 m 1517 gt 1,1,4,7-tetramethylindan, produced vby the cyclo-addi- 25/25=-0.9206. tion of isoprene to para xylene in the presence of sulfuric Analysis calcd for CIGHM: C H Found; 50 acid using the molar ratios and operating conditions dis- C 8903; H closed in Examples 1 and 4 above, was nitrated with mixed Infrared and nuclear magnetic resonance Spectra and acid following the technique disclosed n Examples 1 :and the vapor-phase chromatograrn indicate that the pr 4. A pale yellow, odorless, dinitroderivative, 5,6-din1tronot has the structure noted above and its purity is higher 1,11:47'tetmmeth3hndan, was obtamed (96% y Wgm, M.P. 131.5-1325" (from methanol). The compound was than 90%.

The acetyl derivative, C H O, a White colorless solid, actwe as a Pre'emergence herblcldecrystallized from methanol, melted at 5556 and had A7lalysls-ca1d for H 16 2 4 3 6-10; a mild muskdike 0d N, 10.60. Found: c, 59.48; H, 6.27; N, 10.34.

10.11 Example 9.-1,1-dimetJzyl-5,7-dinitr0-6-ethylindan Nitration of the hydrocarbon with mixed acid by the l,1-dimethyl-6-ethylindan, made by the procedure of technique described above in Example 1 produced in good US. Patent 3,078,319, was nitrated with mixed acid, folyield a dinitro-derivative, pale yellow crystals, M.P. 126 lowing the general procedure disclosed in Examples 1 and 127. 4 above, to produce the pale yellow, odor-less, dinitro- Analysis.-Calcd. for c d-1 N 0 C, 62.71; H, 7.24; derivative, 1,l-dimethyl-5,7-dinitro-6-ethylindan, M.P. 90 N, 9.14. Found: C, 62.75; H, 7.14; N, 9.12. 91.

. Analysis.Calcd. for C H N O C, 59.07; H, 6.09; if;' b N 10.60. Found: c 59.41; H, 6.06; N, 10.22.

, -1zmethylmdan This compound exhibited activity as a pre-emergence Into the steel bottle of the Parr laboratory hydrogelllai herbicide. tor was charged 120 g. of ethanol, 5 g. of Raney nic e and 5 g. of 5,6-dinitro-7-isopropyl-1,1,4-trimethylindan Emmp 1e 1O 57'dmm011246'penmmethylmdan (Example 4 above). Hydrogenation was effected at 72 l,1,2,4,6-pentamethylindan, produced by the cyclo-adto 74 using 50 p.s.i. hydrogen pressure. Nearly the dition of 2,3-dimethyl-1,3-butadiene to met-a xylene in the theoretical amount of hydrogen was absorbed. Upon 75 presence of sulfuric acid using the molar ratios and op- ,erating conditions disclosed in Examples 1 and :4 .abovej,=

I tee to. ;15 fend stirring was: continued 1 be r; onigefr at; 2 The. batch was quenchedincoid wat The :oil which separated was taken up in benzene: and f washed successively with :Water (3 x :100; 1111:}, 5% i set f .diumhydroxide solution 13 x .100 m1.) and again Withterf emit near "va poration iot the beiizefi tee;

( wr 32.3) wares didnot cry t'a 1 ise a e: t -eme e i i T'seompoundexhibrt 1 ms eceh t i ee Ex dm'pte 1.2; as...

using the; sam nitratigr mixture 11 conditiop as: ernq pies/ed in; thei preceding xaniple. he tw'ork up was aetly the; same i he iyield of. crude yellowed was 536g; ob ss-+ c. bu y .1; of: us. :Patent 3,078,319; was narrated mixedi ac e ne 01 a -fi s a dope at nditions sgiv Ari-Examples land 4 o; produce the pale yello dinitroderiva 4 1dan;,;MP

. i. "m mmies: I eabovei compound was ioundto be 1,46,? e ameth ylinda sulfuric acid-catalyzed cy'cl' 'z-addi tion of isoprerie to pee documene using theimolar ratios and operating condit-io s given; inzthe firstiparts of .exam tes; 51g and i4,;w;:;s m; rated using, @1165 acetic acid-acetic vanhyldride-i:ritii;c ac

Kture. as in the .two preceding examples; The: product- 1.5 g.) ;(theory: 53:1); was: a pale yellow; odorlessgwi cons oil: whichcould not be induced-to crystallize iThIS .GIiIde aliqlliid product is suitable, without fiirthe' purl ion, as: ase'leeitive ire-emergence herbicide: f I f y a an 1 5 1i,1+diuiethy1-4eth f-isop'rjopyliudan, prepared byithe. cycloeaddition of isoprene to p-ethylcurnenein' the-presence: of sulfuric; acid using the molar ratios and operating co 2ditious: discliosed: in the first; parts of Exampies' lane 4 b e-Y k snitra e i hmix deeiciustngthemoiar raties I E I Y Y 2 Y 1: 1 1 Y 1 1a.;

i and operating conditions as disclosed above in Examples 1 Exampie 7 lsoplopyl t'lmethylmdan and 4, to produce the golden yellow, odorless, dinitro- 7-isopropyl-1,1,4-trimethylindan, prepared as described derivative, 1,1-dim hy1- y 7 P PYI- in Example 4, was nitrated, using the acetic acid-acetic indan, M.P. 167-168". anhydride-nitric acid mixture and operating conditions Aizalysis.Calcd. for C ,;H N O C, 62.38; H, 7.24; similar to those described in Example 16, to give the yel- N, 9.14. Found: C, 62.94; H, 7.12; N, 9.11. low, odorless, mononitro derivative, 7-isopropyl-5-nitro- This compound is useful as a pre-emergence selective 1,1,4-t i th 1i d M,P 115 116, herbicide. Analysis.Calcd. for C H NO C, 72.84; H, 8.56;

r N, 5.66. Found: C, 72.57; H, 8.93; N, 5.52. Example f" The nitro compound above is active as a pre-emergence mztlomdan herbicide.

4,6-diisopro l 1,1 dirnethylindan, produced by the l cyclo-addition d f isopreneto m-diisopropylbenzene in the Example 5 ethyl 6-mt'OLlfijtehamethylmdan presence of sulfuric acid using the molar ratios and OP- 55 5-ethyl-1,1,3,3-tetramethylindan (S. H. Weber, I. Stofcrating conditions as given in the first parts of Examples berg, D. B. Spoelstra and R. J. C. Kleipool, Rec. trav- 1 and 4 above, was nitrated with mixed acid, as in the chim., 75, 1441 (1956)) was nitrated, using the general above examples, to produce the pale yellow, odorless, method of Example 16, to produce the mono-nitro derivadinitroderivative, 4,6-diisopropyl-l,l-dimethyl-5,7-dinitro tive, 5-ethyl-6-nitro-1,1,3,3-tetramethylindan, a pale yelindan, M.P. 105106. low solid, M.P. 64.5-66.

Analysis.-Calcd. for C I-1 N 0 C, 63.71; H, 7.58; Analysis.Calcd. for C H O N: C, 72.84; H, 8.56; N, 8.74. Found: C, 62.13; H, 6.89; N, 9.29. N, 5.66. Found: C, 72.52; H, 8.69; N, 5.64.

The compound is useful as a pre-ernergence herbicide. The product is useful as a selective pre-emergence Example I5.5-t-butyl-4,6-dinilr0-1,1-dimethyl-7- herblclde' isopropylindan Example 2].4,6-diis0pr0pyZ-1,1-dimethyl-5-nitr0indan S-t-butyl-l,1-dimethyl-7-isopropylindan, produced by the 4,6-diisoproyl-1,1-dimethylindan, prepared as in Excyclo-addition of isoprene to p-t-butylcumene in the ample 13, was mononitrated by the technique used in Expresence of sulfuric acid using molar ratios and operating ample 16 to yield a derivative which was part oil and part conditions of the general procedure disclosed in the first crystalline. The crystalline portion Was separated and part of Examples 1 and 4, was nitrated with mixed acid, purified by recrystallization from methanol yielding 4,6- as in the above exmiples, to produce a pale yellow, odordiisopropyl-l,l-dimethyl-S-nitroindan, pale yellow, odorless, dinitroderivative, M.P. 187204. less crystals, M.P. 121.2-122".

This compound is effective as a selective pre-emergence Analysis.Calcd. for C H NO C, 74.14; H, 9.15;

herbicide. N, 5.09. Found: C, 74.31; H, 9.10; N, 5.48.

This crystalline product, as Well as the portion of the product, is active as a pre-emergence herbicide.

Example 22.-4,6-dinitro--ethyl-I,1,3,3-tetramethylindan 5-ethyl-l,l,3,3-tetramethylindan (S. H. Weber, I. Stofberg, D. B. Spoelstra, and R. J. C. Kleipool, Rec. trav. chim., 75, 1441 (1956)), was nitrated with mixed acid, using the molar ratios and operating conditions of Example 1, above, to produce the pale-yellow dinitroderivative 4,6 dim'tro 5-ethyl 1,1,3,3 tetramethylindan, M.P. l23.5-124.5, which has a strong musk-like odor.

Analysis.-Calcd. for C H O N C, 61.63; H, 6.90; N, 9.58. Found: C, 61.85; H, 6.82; N, 9.42.

This product is useful as a pre-emergence herbicide.

Example 23.4,6-dinitr0-2-ethyl-1,1,3,3,5-pentamethylindan 2-ethyl 1,1,3,3,5 pentamethylindan, prepared by the procedure of Weber 'et al., Rec. trav. chim., 75, 1441 (1956), was nitrated with mixed acid, using the molar ratios and operating conditions of Example 1 above, to produce the pale-yellow dinitroderivative, 4,6-dinitro-2- ethyl-1,1,3,3,5-pentarnethylindan, M.P. 80.0-81.5, which has a musk-like odor.

Analysis.Calcd. for C H N O C, 62.38; H, 7.24; N, 9.14. Found: C, 62.20; H, 7.25; N, 8.89.

This product is useful as a pre-emergence herbicide.

Example 24.4,7-dinitr0-6-ethyl-1,1,3,3,5-pentamethylindan 6-ethyl-l,1,3,3,5-pentamethylindan, prepared by the procedure of Weber et al., Rec. trav. chim., 76, 199 (1957), was nitrated with mixed acid, using the molar ratios and operating conditions of Example 1 above, to produce the pale-yellow, odorless, dinitro-derivative, 4,7-dinitro-6- ethyl-1,l,3,3,5-pentamethylindan, M.P. 144.4-146. The product is active as a plant growth regulant and preemergence herbicide.

Example 25.6-ethyl-4-(and 7-) nitr0-1,1,3,3,5- pentamethylindan 6-ethyl-1,1,3,3,5-pentamethylindan (Weber et al., loc. cit.) was nitrated by the procedure given in Example 16 to produce a pale-yellow viscous mononitro derivative which could not be induced to crystallize. This crude liquid product is useful, Without further purification as a selective pre-emergence herbicide.

Example 26.6-cycl0hexyl-1,1-dimethyl-5-7-dinitr0indan Cyclo-addition of isoprene (2-methyl-l,3-butadiene) to cyclohexylbenzene in the presence of sulfuric acid was eiiected by the general method disclosed above in Examples 1 and 4, to produce 6-cyclohexyl-1,1-dimethylindan, a colorless liquid, B.P. 132 (2 mm.), n 1.5311. This hydrocarbon was nitrated with mixed acid, using the molar ratios and operating conditions given in Examples 1 and 4 above, to produce the pale-yellow, nearly colorless, odorless dinitroderivative, 6-cyclohexyl-1,1-dimethyl5,7- dinitroindan, M.P. -176.

This product shows activity as a plant-growth regulant and pre-emergence herbicide.

The foregoing illustrates the practice of this invention, which however, is not to be limited thereby but is to be construed as broadly as permissible in view of the prior art and limited solely by the appended claims.

We claim:

1. A member selected from the group consisting of:

(a) a compound coming within the scope of the following general formula:

(NA )n wherein R is a member selected from the group consisting of H, and alkyl radicals having from 1 to 3 carbon atoms; R is a member selected from the group consisting of alkyl radicals having from 1 to 5 carbon atoms and cycloalkyl radicals; A is a member selected from the group consisting of O and H with the proviso that at least one A must be 0; m is an integer from 2 to 3; n is an integer from 1 to 2, the sum of m-i-n not exceeding 4, with the proviso that at least one R must be H and the further proviso that where more than two of the R s are H, then m can be an integer from 1 to 3;

(b) 4,6-dinitro-2-ethyl-1,1,3 ,3 ,5 -pentamethylindan and (c) 4,6-dinitro-5-ethyl-1,1,3,3-tetramethylindan.

2. 5,7-dinitro-1,1,4,6-tetramethylindau.

3. 4,6-dinitro-2-ethyl-1,1,3,3,5-pentamethylindan.

4. 4,6-dinitro-5-ethyl-1,1,3 ,3-tetramethylindan.

5. 1,1-dimethyl-5,7-dinitro-6-isopropylindan.

6. 4,6-diisopropyl-1,l-dimethyl-SJ-dinitroindan.

References Cited by the Examiner Grampoloif, Helva, Chem. Acta, vol. 38, pages 1263- 1268 (1955).

Kolodkina et al., Chem. Abs., vol. 59, pages 5083- 5084 (1963).

Barnes et' al., J. Am. Chem. Soc., vol. 74, pages 4199- 4200 (1952).

BENJAMIN R. PADGETT, Acting Primary Examiner.

REUBEN EPSTEIN, LEON D. ROSDOL, Examiners.

L. A. SEBASTIAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,283,016 November 1, 1966 Thomas P. Wood et alt It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 3 and 4, lines 11 to 21, the left-hand portion of the formula should appear as shown below instead of as in the patent:

column 10, line 54, for "l,l,l,4,7" read 1,l,4,7 column 13, line 1, for "portion" read oily portion line 25, for "C read C column 14, line 50, for "A must be 0" read A must be 0 Signed and sealed this 24th day of October 1967.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF: (A) A COMPOUND COMING WITHIN THE SCOPE OF THE FOLLOWING GENERAL FORMULA: 1,1,2,2,3,3-HEXA(R1-),(R2)M-,(NO2)N-INDAN WHEREIN R1 IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF H, AND ALKYL RADICALS HAVING FROM 1 TO 3 CARBON ATOMS; R2 IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKYL RADICALS, A IS A MEMBER CARBON ATOMS AND CYCLOALKYL RADICALS; A IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF O AND H WITH THE PROVISO THAT AT LEAST ONE A MUST BE 0; M IS AN INTEGER FROM 2 TO 3; N IS AN INTEGER FROM 1 TO 2, THE SUM OF M+N NOT EXCEEDING 4, WITH THE PROVISO THAT AT LEAST ONE R1 MUST BE H AND THE FURTHER PROVISO THAT WHERE MORE THAN TWO OF THE R1''S ARE H, THEN M CAN BE AN INTEGER FROM 1 TO 3; (B) 4,6-DINITRO-2-ETHYL-1,1,3,3,5-PENTAMETHYLINDAN AND (C) 4,6-DINITRO-5-ETHYL,-1,1,3,3-TETRAMETHYLINDAN. 